TWI438245B - Film-forming organopolysiloxane emulsion composition - Google Patents

Description

Membrane-forming organic polyoxyl emulsion composition

The present invention relates to an emulsion composition which can form an organic polyfluorene oxide film simply by removing water without the need for an organic metal catalyst such as an organotin catalyst.

The organic polyfluorene which is cured and crosslinked to form a rubber or resin film is used as a surface coating composition on various substrates such as woven fabric, wood and rubber, a binder of a functional inorganic filler such as photocatalyst, and a coating composition Additives for the object. Most of these curable epoxy resins are compositions containing a metal compound such as a tin catalyst as disclosed in JP-A 5-098579, JP-A No. 2005-325253, and JP-A No. 2007-051236. However, this metal compound such as tin catalyst has safety problems.

A silicone elastomer emulsion containing MQ resin is known from WO 2005/040250, which is free of metal compounds such as tin catalyst. In this emulsion, an organofunctional siloxane is used in combination with a ruthenium oxide elastomer for ease of emulsification and improvement of stability. Since this ingredient does not participate in cross-linking, it is quite disadvantageous for film characteristics.

List of citations

Patent Document 1: JP-A 5-098579

Patent Document 2: JP-A 2005-325253

Patent Document 3: JP-A 2007-051236

Patent Document 4: WO 2005/040250 (JP-A 2007-508413)

SUMMARY OF THE INVENTION An object of the present invention is to provide an emulsion composition having high stability which can be simply formed by drying to form an organic polyfluorene oxide film having rubber strength, although in the absence of a metal compound such as a tin catalyst.

The inventors have found a film-forming organic polyoxyxide emulsion composition comprising (A-1) a hydroxyl group-terminated organopolyfluorene represented by the general formula (I) and a composition represented by the formula (II) a reaction product comprising a trialkyl decyloxy group and a decanoate unit and an organopolyfluorene having a decyl group, and (A-2) vermiculite, or (A-3) represented by the formula (I) a hydroxyl group-terminated organopolyfluorene and an organopolyoxyl group having a trialkyldecyloxy group and a decanoate unit and having a decyl group represented by the formula (II) and having a sterol group on the surface thereof The reaction product of vermiculite, (B) emulsifier, and (C) water remain completely stable, free from metal compounds such as tin catalyst, and can be easily dried to form an organic polyfluorene oxide film having rubber strength.

It is to be noted that the inventors have proposed an emulsion composition comprising a reaction product of a hydroxyl group-terminated oxirane and an MQ resin which is emulsified together with a water-miscible organic solvent (Japanese Patent Application No. 2007-285785). What we want to further improve the strength of the dry rubber film of this composition.

The first specific embodiment provides a film-forming organic polyoxyxide emulsion composition comprising: (A-1) 100 parts by weight of a hydroxyl group-terminated organopolyfluorene represented by the formula (I) The reaction product of the composition of the formula (II) comprising a trialkyl decyloxy group and a decanoate unit and an organic polyoxo group having a decyl group, (A-2) 0.1 to 20 parts by weight of vermiculite, (B) 1 to 50 parts by weight of an emulsifier, and

(C) 25 to 20,000 parts by weight of water.

The formulae (I) and (II) are: HO-[R ¹ ₂ SiO] _n -H (I) wherein R ¹ is a monovalent organic group of 1 to 20 carbon atoms, a hydroxyl group or hydrogen, and n is 2 to a positive number of 5,000, and

[R ² ₃ SiO _1/2 ] _a [R ² ₂ SiO _2/2 ] _b [SiO _4/2 ] _c (II) wherein R ² is a monovalent organic group of 1 to 20 carbon atoms, a hydroxyl group or hydrogen, a, b and c are positive numbers in the following ranges: 0.1 a 0.7,0 b 0.5, 0.3 c 0.7, and a+b+c=1.

A second specific embodiment provides a film-forming organic polyoxyxide emulsion composition comprising: (A-3) 100 parts by weight of a hydroxyl group-terminated organopolyfluorene represented by the formula (I) a reaction product of the composition (II) comprising a trialkyldecyloxy group and a niobate unit and an organopolyfluorene having a decyl group and a vermiculite having a sterol group on the surface thereof, (B) 1 to 50 parts by weight of emulsifier, and

(C) 25 to 20,000 parts by weight of water.

The film-forming organic polyoxyxide emulsion composition of the first and second embodiments may additionally comprise (D) from 1 to 50 parts by weight of a water-miscible organic solvent having an SP value in the range of from 8.0 to 11.0.

As used herein, the term "hydroxy-terminated organopolyoxy" refers to an organopolyoxy group having a hydroxyl group attached at either end.

The beneficial effects of the invention

The emulsion composition of the present invention has an advantage that an organic polyfluorene oxide film having rubber strength can be formed simply by drying the composition without requiring an organic metal catalyst. In addition, the emulsion is completely stable.

Description of specific embodiments

The component (A-1) is a reaction product of a hydroxyl group-terminated organic polyfluorene oxide and an organic polyfluorene oxide containing a trialkylmethoxy group and a decanoate unit and a decyl group. It is prepared by reacting a hydroxyl group-terminated organopolyfluorene with an organopolyoxane group containing a trialkyldecyloxy group and a decanoate unit and having a decyl group.

A reactant, a hydroxyl terminated organic polyoxo group represented by the general formula (I): HO-[R ¹ ₂ SiO] _n -H (I) wherein R ¹ is a monovalent organic group of 1 to 20 carbon atoms Group, hydroxyl or hydrogen, and n is a positive number from 2 to 5,000.

Specifically, R ¹ is a monovalent organic group, a hydroxyl group, and a hydrogen atom selected from 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. Examples of the C ₁ -C ₂₀ monovalent organic group include a linear, branched or cyclic alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, fluorene. Base, dodecyl, tetradecyl, hexadecanyl, octadecyl, cyclopentyl, cyclohexyl and cycloheptyl; aryl, such as phenyl, tolyl and naphthyl; alkenyl, such as vinyl and alkenyl Alkyl; alkoxy, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, and octyloxy; an epoxy group-containing monovalent hydrocarbon group, such as 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl; amine-containing monovalent hydrocarbon groups such as 3-aminopropyl, N-(2-aminoethyl)-3- Aminopropyl, N-(1,3-dimethylbutylidene)-3-aminopropyl and N-phenyl-3-aminopropyl; and a mercapto group-containing monovalent hydrocarbon group such as 3-mercaptopropyl. Preferably, at least 80 mole % of R ¹ is methyl.

The subscript n is a positive integer from 2 to 5,000. The organopolyfluorene of formula (I) wherein n is greater than 5,000 is less reactive with organopolyoxo or vermiculite comprising trialkyldecyloxy and decanoate units. Preferably n is a positive integer of from 10 to 3,000, and more preferably from 30 to 1,000.

Another reactant comprising a trialkyldecyloxy group and a decanoate unit and an organic polyoxo group having a decyl group is represented by the composition formula (II): [R ² ₃ SiO _1/2 ] _a [R ² ₂ SiO _2/2 ] _b [SiO _4/2 ] _c (II) wherein R ² is a monovalent organic group of 1 to 20 carbon atoms, a hydroxyl group or hydrogen, and a, b and c are positive numbers in the following ranges: 0.1 a 0.7,0 b 0.5, 0.3 c 0.7, and a+b+c=1.

Specifically, R ² is a monovalent organic group selected from 1 to 20 carbon atoms, a hydroxyl group, and a hydrogen atom. Examples of the C ₁ -C ₂₀ monovalent organic group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a dodecyl group, and a decyl group. Tetrakis, hexadecyl, octadecyl, cyclopentyl, cyclohexyl and cycloheptyl; aryl, such as phenyl, tolyl and naphthyl; alkenyl, such as vinyl and allyl; alkoxy, Such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy and octyloxy; epoxy groups such as 3-glycidoxypropyl and 2-( 3,4-Epoxycyclohexyl)ethyl; amines such as 3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl, N-(1,3-dimethyl Butylene)-3-aminopropyl and N-phenyl-3-aminopropyl; and fluorenyl, such as 3-mercaptopropyl. Preferably, at least 80 mole % of R ² is methyl.

Subscripts a, b and c are positive numbers in the following ranges: 0.1 a 0.7,0 b 0.5, 0.3 c 0.7, and a+b+c=1, and preferably 0.2 a 0.6,0 b 0.4, 0.4 c 0.6, and a+b+c=1.

These organopolyfluorenes containing trialkyl decyloxy and decanoic acid units are well known in the art, and among them, R ² is a methyl group and b = 0 is a well-known MQ resin. In organic polyfluorenes containing trialkyl decyloxy and decanoate units, the sterol group leaves a small amount. Then, a condensation reaction can be carried out between the remaining sterol groups and the hydroxyl group on the hydroxyl group-terminated organic polyfluorene or the surface hydroxyl group on the vermiculite described later to form a desired reaction product.

In order to increase the sterol group content in the organopolyfluorene containing the trialkyl decyloxy group and the decanoate unit, it is effective to incorporate the [R ² ₂ SiO _2/2 ] unit system in the organopolyfluorene oxide. When the trialkyl decyloxy phthalate is prepared from a reactant such as trialkyl chlorodecane and water glass, the [R ² ₂ SiO _2/2 ] unit can be used in addition to ordinary reactants according to well-known techniques. Dialkyldichloromethane is incorporated by synthesis. In the case of incorporating a [R ² ₂ SiO _2/2 ] unit, the value of b is 0.001. b 0.5. If b is more than 0.5, the reaction product becomes less likely to form a film. Then b must be equal to or less than 0.5.

From the viewpoint of reactivity, a sterol group content of preferably 0.01 to 2 mol/100 g of the organopolyoxane of the formula (II) is preferred.

The hydroxyl group-terminated organopolyfluorene and the organopolyoxyl group containing a trialkyldecyloxy group and a decanoate unit are mixed in a ratio of between 20/80 and 90/10 by weight. If the ratio of the hydroxyl group-terminated organopolyfluorene is less than 20, the reaction product may become a resin powder rather than a film. If the ratio of the hydroxyl group-terminated organopolyfluorene is more than 90, the reaction product may become a paste or an oil. To this end, the ratio of the hydroxyl-terminated organopolyfluorene to the organopolyoxyl containing the trialkyldecyloxy group and the decanoate unit should be between 20/80 and 90/10 by weight. The range is preferably between 30/70 and 85/15 by weight.

When the ammonium or amine compound is used as a catalyst, the reaction of the hydroxyl group-terminated organopolyfluorene with the organopolyfluorene containing the trialkyldecyloxy group and the decanoate unit can be quickly performed even at room temperature. get on. Examples of the catalyst include ammonia; ammonium compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide; monoalkylamines such as methylamine, Ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine and decylamine; dialkylamines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentane Amine, dihexylamine, diheptylamine, dioctylamine, diamine and diamine; and trialkylamines such as trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexyl Amine, triheptylamine, trioctylamine, tridecylamine and tridecylamine. From the viewpoint of the reaction rate and emulsion stability, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, butylamine, hexylamine, octylamine, tripropylamine and tributylamine are preferred.

The amount of the catalyst used is 0.1 to 10 parts by weight per 100 parts by weight of a combination of a hydroxyl group-terminated organopolyfluorene oxide and a trioxinoxy group and a decanoate unit and an organopolyoxy group having a decyl group. . Beyond this range, a smaller amount of catalyst may not contribute to the condensation reaction or final film formation, while a larger amount of catalyst may adversely affect the stability of the emulsion.

A suitable reaction temperature is 0 to 50 ° C, and more preferably 5 to 30 ° C, and an appropriate reaction time is 3 to 100 hours, and more preferably 6 to 50 hours. At the end of the reaction, the reaction mixture can be neutralized with an acidic compound as the emulsion will become more stable. Exemplary acidic compounds include acetic acid, formic acid, phosphoric acid, hydrochloric acid, sulfuric acid, and dodecylsulfonic acid.

Since the reaction product of the hydroxyl group-terminated organic polyfluorene oxide and the organic polyfluorene oxide containing the trialkylsulfoxy group and the decanoate unit becomes a film, it is difficult to emulsify the reaction product. It is therefore preferred that both the hydroxyl-terminated organopolyfluorene and the organopolyoxyl containing the trialkyldecyloxy and decanoate units are pre-emulsified and reacted in the emulsion.

Ingredient (A-2) is a vermiculite, represented by SiO ₂ , which includes finely divided vermiculite and colloidal vermiculite and is used to enhance the strength of the rubber film. The finely divided vermiculite is preferably an untreated (unsurface treated) hydrophilic vermiculite. The finely divided vermiculite can be used alone or in a mixture of two or more species.

Examples of the hydrophilic vermiculite include wet vermiculite such as sedimentary vermiculite and colloidal vermiculite, and dry vermiculite such as silica xerogel and soot. Illustrative examples include Aerosil (Nippon Aerosil Co., Ltd.), Nipsil And Nipgel (Tosoh Silica Co., Ltd.) and Sylysia (Fuji Silysia Chemical Co., Ltd.). It is also possible to use vermiculite whose surface is treated with decane or a decyloxy compound having a triorganomethoxy group or a diorganomethoxy group to improve the affinity of the vermiculite to the hydroxyl group-terminated organopolyoxygen.

There is no limit to the type of colloidal vermiculite. Typically, it has a particle size of 5 to 50 nm and is stabilized with sodium, ammonium or aluminum. Colloidal vermiculite available herein is commercially available under the tradename Snowtex from Nissan Chemical Industries, Inc., Ludox from WR Grace & Co., Silicadol from Nippon Chemical Industrial Co., Adelite AT from Adeka Ltd. and Cataloid S. Catalysts & Chemicals Purchased by Industries Ltd.

The finely divided vermiculite preferably has a specific surface area of at least 100 m ² /g, and more preferably 150 to 500 m ² /g, as measured by the BET method. Vermiculite having a specific surface area of less than 100 m ² /g may have a small membrane strengthening effect.

A suitable amount of the component (A-2) to be mixed is 0.1 to 20 parts by weight per 100 parts by weight of the component (A-1). Less than 0.1 part of the component (A-2) will result in a dry film having a low rubber strength and more than 20 parts of the component (A-2) will result in a hard brittle film. Thus, the amount of the component (A-2) to be mixed should be 0.1 to 20 parts (preferably 0.2 to 15 parts, and more preferably 0.3 to 10 parts by weight) per 100 parts by weight of the component (A-1).

If the vermiculite is used as the component (A-2), the reaction of the hydroxyl group-terminated organopolyoxygen with the trialkyldecyloxy group and the decanoate unit and the organopolyoxyl group having a decyl group is used to produce the component. (A-1), a further improvement in the strength of the rubber film is expected. Thus, it is advantageous to use (A-3) a hydroxyl group-terminated organopolyoxygen, a reaction product comprising a trialkyldecyloxy group and a decanoate unit and an organic polyfluorene having a sterol group and a vermiculite instead of a component. A mixture of (A-1) and (A-2).

The reaction product (A-3) is derived from the hydroxyl group on the hydroxyl group-terminated organopolyfluorene, the residue containing the trialkyldecyloxy group and the niobate unit and the organopolyfluorene having a decyl group. A condensation reaction between an alcohol group and a hydroxyl group (or a sterol group) on the surface of the vermiculite.

In this embodiment, the proportion of the hydroxyl group-terminated organopolyoxy group for the reaction comprising the trialkyldecyloxy group and the decanoate unit and the organopolyfluorene having a decyl group is as the first specific The examples are between 20/80 and 90/10 by weight and preferably between 30/70 and 85/15 by weight. If the ratio of the hydroxyl group-terminated organopolyfluorene is less than 20, the reaction product may become a resin powder rather than a film. If the ratio of the hydroxyl group-terminated organopolyfluorene is more than 90, the reaction product may become a paste or an oil.

The ratio of the hydroxyl group-terminated organopolyfluorene for the reaction and the organopolyxylene-containing vermiculite containing the trialkyldecyloxy group and the decanoate unit and the decyl group is such that the vermiculite is present in an amount of 0.1. Up to 20 parts by weight per 100 parts by weight of a combination of a hydroxyl group-terminated organopolyfluorene oxide and an organopolyfluorene containing a trialkyldecyloxy group and a decanoate unit and a decyl alcohol group. According to this standard, less than 0.1 part of vermiculite results in a dry film having a low rubber strength and more than 20 parts of vermiculite results in a hard brittle film. The amount of vermiculite should then be from 0.1 to 20 parts (preferably from 0.2 to 15 parts, and more preferably from 0.3 to 10 parts by weight) per 100 parts by weight of the combined organopolyoxyl.

Ingredient (B) is an emulsifier. The emulsifier is not particularly limited as long as it promotes emulsification and dispersion of the reaction product of the hydroxyl group-terminated organopolyoxygen with the trialkyldecyloxy group and the decanoate unit. . Exemplary emulsifiers include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene propylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, and polyoxyethylene fatty acid esters; anionic surfactants Such as alkyl sulfates, alkyl benzene sulfonates, alkyl sulfosuccinates, alkyl phosphates, polyoxyethylene alkyl ether hydrogen sulfate and polyoxyethylene alkyl phenyl ether hydrogen sulfate Esters; cationic surfactants such as quaternary ammonium salts and alkylamine acetates; amphoteric surfactants such as alkyl betaines and alkyl imidazolines; and water soluble polymers such as polyvinyl alcohol.

From the viewpoint of stability (in the middle), preferred are nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene propylene alkyl ethers, and polyoxyethylene alkylphenyl ethers. Illustrative, non-limiting examples include polyoxyethylene octyl ether, polyoxyethylene decyl ether, polyoxyethylene decyl ether, polyoxyethylene propylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene propylene lauryl ether, Polyoxyethylene tridecyl ether, polyoxyethylene propylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, Polyoxyethylene nonylphenyl ether and polyoxyethylene styrenated phenyl ether. These emulsifiers may be used singly or in combination of two or more.

More preferably, a small amount of anionic surfactant is used in combination with the nonionic surfactant because this combination is effective to keep the emulsion more stable.

The component (B) should be added in an amount of from 1 to 50 parts by weight per 100 parts by weight of the component (A-1). Less than 1 part of the component (B) will be insufficient to emulsify and more than 50 parts may detract from film formability. The preferred amount of the component (B) is 2 to 30 parts, and more preferably 3 to 20 parts by weight per 100 parts by weight of the component (A-1). In an alternative embodiment in which the component (A-3) is used instead of the mixture of the components (A-1) and (A-2), the component (B) should be added in an amount of from 1 to 50 parts (preferably from 2 to 30 parts). And more preferably 3 to 20 parts by weight) per 100 parts by weight of the component (A-3).

In the organic polyoxyxide emulsion composition of the present invention, water is used as the component (C). The amount of water as the component (C) should be 25 to 20,000 parts (preferably 50 to 10,000 parts by weight) per 100 parts by weight of the component (A-1). Beyond this range, an emulsion containing a small amount of water has a higher viscosity and becomes an emulsion which cannot be efficiently processed and contains a relatively large amount of water becomes less stable. In an alternative embodiment in which the component (A-3) is used instead of the mixture of the components (A-1) and (A-2), the amount of the component (C) should be 25 to 20,000 parts (preferably 50 to 10,000 parts by weight). ) / 100 parts by weight of the component (A-3).

In the practice of the present invention, it is preferred to carry out the reaction for producing the reaction product (A-1) or (A-3) in the components (B) and (C). By carrying out the reaction in this manner, an emulsion composition within the scope of the present invention is obtained. More specifically, the component (A-1), that is, the reaction product of the organopolyfluorenyl oxide of the formula (I) and the organopolyfluorinated oxygen of the formula (II) can be obtained by the following means: in the component (B) and C) Emulsifying the mixture of the diorganopolyoxynium and allowing the organopolyfluorenes to react with each other in the emulsion under the above reaction conditions. The vermiculite is then added to the reaction mixture as component (A-2) to produce an emulsion composition within the scope of the present invention.

The component (A-3), that is, the reaction product of the organopolyfluorene of the formula (I), the organopolyoxane of the formula (II) and vermiculite can be obtained by the following means: in the components (B) and (C) Emulsifying a mixture of the diorganopolyoxymethane and vermiculite, and allowing the organopolyphosphorus and vermiculite to react with each other in the emulsion under the above reaction conditions; or emulsifying in components (B) and (C) a mixture of the diorganopolyoxane, dispersing the finely divided vermiculite in a hydrophilic solvent such as ethylene glycol, adding the dispersion to the emulsion, and allowing the organopolyfluorene and the finely divided vermiculite to interact with each other The emulsion is reacted under the above reaction conditions. In either case, an emulsion composition within the scope of the invention is obtained.

In the organic polyoxyxide emulsion composition, a water-miscible organic solvent having an SP value in the range of 8.0 to 11.0 is preferably added as component (D) to further improve emulsion stability. As used herein, the term "SP value" refers to a solubility parameter, which is proposed by Hildebrand, to indicate a measure of miscibility between liquids. If an organic solvent having an SP value of less than 8.0 or greater than 11.0 is used, the emulsion will become less stable when emulsified. Therefore, the SP value should be in the range of 8.0 to 11.0, and preferably in the range of 8.5 to 10.5. The organic solvent should be water miscible. If the organic solvent is not water-miscible, the emulsion will become less stable when emulsified. The term "water miscible" means a solubility of at least 1 g, preferably at least 2 g, in 100 g of water at 20 °C.

Typical water-miscible organic solvents include alcohol compounds, ketone compounds, ester compounds, and ether compounds. Illustrative examples include 赛路苏, 赛赛路苏, 丁赛路苏, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, carbitol, carbitol, Propyl carbitol, butyl carbitol, celecoxib acetate, butyl succinate acetate, propylene glycol monomethyl ether acetate, carbitol acetate, butyl carbitol acetate and 2, 2,4-Trimethyl-1,3-pentanediol monoisobutyrate. In particular, preferred are Ding Lucu, butyl races acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and 2,2,4-trimethyl-1,3-pentanediol. Monoisobutyrate.

The component (D) is appropriately added in an amount of from 1 to 50 parts by weight per 100 parts by weight of the component (A-1). Less than 1 part of ingredient (D) provides poor emulsion stability. More than 50 parts of ingredient (D) does not adversely affect the properties of the emulsion, but it is undesirable that it will volatilize into the environment when in use. The component (D) is preferably added in an amount of 2 to 40 parts by weight (more preferably 3 to 30 parts by weight) per 100 parts by weight of the component (A-1). In an alternative embodiment in which the component (A-3) is used instead of the mixture of the components (A-1) and (A-2), the amount of the component (D) should be from 1 to 50 parts (preferably from 2 to 40 parts, More preferably, it is 3 to 30 parts by weight) per 100 parts by weight of the component (A-3).

In the organic polyoxyxide emulsion composition of the present invention, various additives may be mixed within a range not to the object of the present invention.

When used, the organic polyoxyxide emulsion composition of the present invention can be applied to the surface of various substrates. The emulsion composition can be applied to the substrate by any of the following prior art coating techniques, including dipping, spraying, rolling, and brushing. Although the coating weight of the organopolyoxyl emulsion composition is not particularly limited, a coating weight of 0.1 to 200 g/m ² , particularly 1 to 100 g/m ² is generally used.

After coating, the organopolyfluorene oxide film can be formed only by drying. The drying step can use any desired conditions under which water and the water-miscible organic solvent will evaporate. Drying can last for 1 to 3 days at room temperature. When heated, the drying can be continued at 100 to 180 ° C for about 1 to 30 minutes.

The organopolyfluorene emulsion composition of the present invention can be used as a coating agent for various substrate surfaces, as a mold release or lubricant for the surface of rubber articles, as a functional inorganic filler such as a photocatalyst adhesive, and a fabric. The feel modifier, but its use is not limited to this.

Example

Embodiments of the invention are provided below by way of illustration and not by way of limitation. In these examples, all percentages are by weight and the viscosity is measured by a Brookfield (BM model) rotational viscometer at 25 °C.

Preparation Example 1

The vacuum stripping apparatus is filled with 1,400 g of a 50% organic polyoxo-containing toluene solution containing a trialkyl decyloxy group and a decanoate unit, which is composed of the formula: [(CH ₃ ) ₃ SiO _1/2 ] _0.39 [SiO _4/2 ] _0.61 (sterol content 0.1 mol/100 g), and 300 g of butyl racere acetate as a water-miscible organic solvent (SP value) 8.9). Toluene was distilled off under vacuum only at 50 ° C and 20 mmHg, yielding a mixture of 1,000 g of organopolyoxyl containing trialkyl decyloxy and decanoate units and the water-miscible organic solvent. . This mixture was a solution having a nonvolatile content of 69.9% and a viscosity of 230 mpa-s when heated at 150 ° C / 3 hours.

Example 1

High speed disperser (Homo Disper Filled with 210 g of a hydroxyl group-terminated organopolyfluorene of the formula HO-[(CH ₃ ) ₂ Si-O] ₄₀₀ -H having a viscosity of 3,000 mpa-s, and 129 g of a trialkylsulfonium-containing Mixture A of an organic polyoxonium group of an oxy group and a decanoate unit with the water-miscible organic solvent (prepared as in Preparation Example 1), 20 g of Noigen XL40 (Dai-Ichi Kogyo Seiyaku Co., Ltd., poly Oxymethenyl ether, HLB 10.5), 23 g of Noigen XL400D (Dai-Ichi Kogyo Seiyaku Co., Ltd., 65% aqueous solution of polyoxyalkylene ether ether, HLB 18.4), 5 g of Newcol 291M (Nippon Nyukazai Co., Ltd., 75 The sodium alkylsulfosuccinate solution) was used as an emulsifier and 589.6 g of deionized water. These ingredients are emulsified into a milky white emulsion. To this emulsion was added 90 g of a dispersion having 20% Aerosil 200 (Nippon Aerosil Co., Ltd.) dispersed in ethylene glycol and 20 g of a 25% aqueous solution of tetramethylammonium hydroxide. The reaction was carried out at 15 ° C for 24 hours, after which 3.4 g of acetic acid was added for neutralization to give a milky white emulsion B. Emulsion B had 29.6% non-volatile content when heated at 150 ° C / 3 hours, and the non-volatile residue was in the form of a film. While remaining at room temperature for 3 months, Emulsion B remained stable without separation.

A certain amount of this emulsion composition was supplied to the pan so that the dry residue had a thickness of 0.7 mm, dried at room temperature for 1 week, and additionally dried at 150 ° C for 2 hours to obtain a rubber sheet. The tensile strength and elongation of the rubber sheet were measured in accordance with JIS K6249. The results are shown in Table 1.

Example 2

High speed disperser (Homo Disper ) 120 g based filling having a viscosity of 3,000 mPa-s of the general formula _{HO - [(CH 3) 2} Si-O] 400 -H of hydroxyl-terminated organopolysiloxanes of silicon oxide, 120 g has a viscosity of 30,000 mPa-s Hydroxyl-terminated amino group-modified organopolymer of the formula HO-[(CH ₃ ) ₂ Si-O] ₁₀₀₀ -[(CH ₃ )Si(C ₃ H ₆ NH ₂ )-O] ₄ -H Oxygen, 86 g of a mixture of an organopolyanthracene containing a trialkyldecyloxy group and a decanoate unit and the water-miscible organic solvent A (as prepared in Preparation Example 1), 20 g of Noigen XL40 (Dai-Ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene ether, HLB 10.5), 23 g of Noigen XL400D (Dai-Ichi Kogyo Seiyaku Co., Ltd., 65% aqueous solution of polyoxyalkylene ether ether, HLB 18.4), 5 g Newcol 291M (Nippon Nyukazai Co., Ltd., 75% sodium sulfosuccinate solution) was used as an emulsifier and 602.6 g of deionized water. These ingredients are emulsified into a milky white emulsion. To this emulsion was added 100 g of a dispersion having 20% Aerosil 200 (Nippon Aerosil Co., Ltd.) dispersed in ethylene glycol and 20 g of a 25% aqueous solution of tetramethylammonium hydroxide. The reaction was carried out at 15 ° C for 24 hours, after which 3.4 g of acetic acid was added for neutralization to give a milky white emulsion C. Emulsion C had 29.7% non-volatile content when heated at 150 ° C / 3 hours, and the non-volatile residue was in the form of a film. While remaining at room temperature for 3 months, Emulsion C remained stable without separation.

A certain amount of this emulsion composition was supplied to the pan so that the dry residue had a thickness of 0.7 mm, dried at room temperature for 1 week, and additionally dried at 150 ° C for 2 hours to obtain a rubber sheet. The tensile strength and elongation of the rubber sheet were measured in accordance with JIS K6249. The results are shown in Table 1.

Example 3

High speed disperser (Homo Disper ) Filled with 210 g based formula HO viscosity of 3,000 mPa-s having a _{- [(CH 3) 2 Si} -O] ₄₀₀ -H organo silicon oxide to the hydroxyl-terminated, 129 g trialkyl silicon containing group And a mixture of the organic polyfluorene and the water-miscible organic solvent of the citrate unit (as prepared in Preparation Example 1), 20 g of Noigen XL40 (Dai-Ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene) Mercaptoether, HLB 10.5), 23 g of Noigen XL400D (Dai-Ichi Kogyo Seiyaku Co., Ltd., 65% aqueous solution of polyoxyalkylene ether ether, HLB 18.4), 5 g of Newcol 291M (Nippon Nyukazai Co., Ltd., 75% alkane Sodium sulfosuccinate solution) as an emulsifier and 589.6 g of deionized water. These ingredients are emulsified into a milky white emulsion. To this emulsion was added 20 g of a 25% aqueous solution of tetramethylammonium hydroxide. The reaction was carried out at 15 ° C for 24 hours, after which 3.4 g of acetic acid was added for neutralization. Separately, 90 g of a dispersion having 20% Aerosil 200 (Nippon Aerosil Co., Ltd.) dispersed in ethylene glycol was added and mixed to produce a milky white emulsion D. Emulsion D had 29.9% non-volatile content when heated at 150 ° C / 3 hours, and the non-volatile residue was in the form of a film. While remaining at room temperature for 3 months, Emulsion D remained stable without separation.

A certain amount of this emulsion composition was supplied to the pan so that the dry residue had a thickness of 0.7 mm, dried at room temperature for 1 week, and additionally dried at 150 ° C for 2 hours to obtain a rubber sheet. The tensile strength and elongation of the rubber sheet were measured in accordance with JIS K6249. The results are shown in Table 1.

Comparative example 1

High speed disperser (Homo Disper ) Filled with 210 g based formula HO viscosity of 3,000 mPa-s having a _{- [(CH 3) 2 Si} -O] ₄₀₀ -H organo silicon oxide to the hydroxyl-terminated, 129 g trialkyl silicon containing group And a mixture of the organic polyfluorene and the water-miscible organic solvent of the citrate unit (as prepared in Preparation Example 1), 20 g of Noigen XL40 (Dai-Ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene) Mercaptoether, HLB 10.5), 23 g of Noigen XL400D (Dai-Ichi Kogyo Seiyaku Co., Ltd., 65% aqueous solution of polyoxyalkylene ether ether, HLB 18.4), 5 g of Newcol 291M (Nippon Nyukazai Co., Ltd., 75% alkane Sodium sulfosuccinate solution) as an emulsifier and 589.6 g of deionized water. These ingredients are emulsified into a milky white emulsion. To this emulsion was added 20 g of a 25% aqueous solution of tetramethylammonium hydroxide. The reaction was carried out at 15 ° C for 24 hours, after which 3.4 g of acetic acid was added for neutralization to give a milky white emulsion E. Emulsion E had a 31.5% non-volatile content when heated at 150 ° C / 3 hours, and the non-volatile residue was in the form of a film. While remaining at room temperature for 3 months, Emulsion E remained stable without separation.

A certain amount of this emulsion composition was supplied to the pan so that the dry residue had a thickness of 0.7 mm, dried at room temperature for 1 week, and additionally dried at 150 ° C for 2 hours to obtain a rubber sheet. The tensile strength and elongation of the rubber sheet were measured in accordance with JIS K6249. The results are shown in Table 1.

Comparative example 2

In addition to replacing the hydroxyl-terminated organopolyoxyl with 120 g of a hydroxyl group having a hydroxyl group as a general formula HO-[(CH ₃ ) ₂ Si-O] ₄₀₀ -H having a viscosity of 3,000 mPa-s Oxygen with 120 g of a formula HO-[(CH ₃ ) ₂ Si-O] ₁₀₀₀ -[(CH ₃ )Si(C ₃ H ₆ NH ₂ )-O] ₄ -H having a viscosity of 30,000 mPa-s The hydroxyl group is a mixture of terminal amino group-modified organopolyoxane, and the procedure of Comparative Example 1 is repeated, and the organic polyfluorene containing a trialkyl decyloxy group and a decanoate unit is organically miscible with the water. The amount of the mixture A of the solvent (prepared as in Preparation Example 1) was 86 g. A milky white emulsion F was obtained. Emulsion F had a non-volatile content of 31.7% when heated at 150 ° C / 3 hours, and the non-volatile residue was in the form of a film. When kept at room temperature for 3 months, the emulsion F remained stable without separation.

A certain amount of this emulsion composition was supplied to the pan so that the dry residue had a thickness of 0.7 mm, dried at room temperature for 1 week, and additionally dried at 150 ° C for 2 hours to obtain a rubber sheet. The tensile strength and elongation of the rubber sheet were measured in accordance with JIS K6249. The results are shown in Table 1.

It has been confirmed that the organic polyfluorene oxide film improves the rubber strength by using a reaction (product) in which a vermiculite is combined with a hydroxyl group-terminated organic polyfluorene oxide and a trialkylsulfonium group and a niobate unit-containing organic polyfluorene oxide. And elongation.

Claims (2)

A film-forming organic polyoxyxide emulsion composition comprising: (A-3) 100 parts by weight of a hydroxyl group-terminated organopolyfluorene represented by the formula (I) and represented by the formula (II) a reaction product comprising a trialkyldecyloxy group and a niobate unit and an organopolyfluorene having a decyl group and a vermiculite having a sterol group on the surface: HO-[R ¹ ₂ SiO] _n -H ( I) a monovalent organic group wherein R ¹ is 1 to 20 carbon atoms, a hydroxyl group or hydrogen, and n is a positive number of 2 to 5,000, [R ² ₃ SiO _1/2 ] _a [R ² ₂ SiO _2/2 ] _b [SiO _4/2 ] _c (II) wherein R ² is a monovalent organic group of 1 to 20 carbon atoms, a hydroxyl group or hydrogen, and a, b and c are positive numbers in the following ranges: 0.1 a 0.7,0 b 0.5, 0.3 c 0.7, and a+b+c=1, (B) 1 to 50 parts by weight of an emulsifier, and (C) 25 to 20,000 parts by weight of water. A film-forming organic polyoxyxide emulsion composition comprising: (A-3) 100 parts by weight of a hydroxyl group-terminated organopolyfluorene represented by the formula (I) and represented by the formula (II) a reaction product comprising a trialkyldecyloxy group and a niobate unit and an organopolyfluorene having a decyl group and a vermiculite having a sterol group on the surface: HO-[R ¹ ₂ SiO] _n -H ( I) a monovalent organic group wherein R ¹ is 1 to 20 carbon atoms, a hydroxyl group or hydrogen, and n is a positive number of 2 to 5,000, [R ² ₃ SiO _1/2 ] _a [R ² ₂ SiO _2/2 ] _b [SiO _4/2 ] _c (II) wherein R ² is a monovalent organic group of 1 to 20 carbon atoms, a hydroxyl group or hydrogen, and a, b and c are positive numbers in the following ranges: 0.1 a 0.7,0 b 0.5, 0.3 c 0.7, and a+b+c=1, (B) 1 to 50 parts by weight of an emulsifier, (C) 25 to 20,000 parts by weight of water, and (D) 1 to 50 parts by weight having an SP value of 8.0 to A water miscible organic solvent in the range of 11.0.